CN114641529A - Method for producing fluorine-containing polymer and composition thereof - Google Patents

Method for producing fluorine-containing polymer and composition thereof Download PDF

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CN114641529A
CN114641529A CN202080076940.2A CN202080076940A CN114641529A CN 114641529 A CN114641529 A CN 114641529A CN 202080076940 A CN202080076940 A CN 202080076940A CN 114641529 A CN114641529 A CN 114641529A
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fluorine
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composition
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CN114641529B (en
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铃木悠希
松浦诚
尾形明俊
白井淳
冈田伦明
芦田汐未
田中义人
岸川洋介
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Daikin Industries Ltd
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Abstract

The invention aims to provide a method for producing a fluorine-containing polymer and a composition thereof. In the present invention, the composition comprises a fluorine-containing polymer (A) having a structural unit of a fluorine-containing aliphatic ring as a main component, wherein the fluorine-containing aliphatic ring of the fluorine-containing polymer (A) has 1,2 or 3 ether type oxygen atoms as ring-forming atoms, and when the fluorine-containing aliphatic ring contains a plurality of the ether type oxygen atoms, the ether type oxygen atoms are not adjacent to each other, and the content of the fluorine-containing polymer (A) is 20% by mass or more based on the mass of the composition.

Description

Method for producing fluorine-containing polymer and composition thereof
Technical Field
The present disclosure relates to a method for producing a fluoropolymer, a composition thereof, and the like.
Background
A fluorine-containing polymer obtained by polymerizing a fluorine-containing monomer having a polymerizable carbon-carbon double bond and an oxygen atom as a ring-forming atom is useful as a coating material for an antireflection film or the like formed on a photoresist layer in a lithography technique.
At CF2＝CFOCF2CF2CF＝CF2CF as a solvent is added to the fluoropolymer obtained by polymerization3CF2CF2CF2CF2CF2CH2CH3In (c), a composition having a fluoropolymer content of 20 mass% was obtained (example 6 of patent document 1).
CF2＝CFCF2CF2OCF＝CF2Copolymerizing with other fluorine-containing monomer in the absence of a solvent to obtain a fluorine-containing polymer (special forExample 2 of patent document 2).
A solution composition containing 10 mass% of a fluoropolymer was obtained (production examples 1 to 7 of patent document 3).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2018-119019
Patent document 2: japanese patent laid-open publication No. 2005-314482
Patent document 3: international publication No. 2013-018730
Disclosure of Invention
Technical problem to be solved by the invention
The main object of the present invention is to provide a method for producing a fluoropolymer and a composition thereof.
Technical solution for solving technical problem
The present invention includes the following embodiments:
item 1:
a composition comprising a fluorine-containing polymer (A) and an aprotic solvent (B), wherein the fluorine-containing polymer (A) contains a structural unit having a fluorine-containing aliphatic ring as a main component,
the fluorine-containing alicyclic ring of the fluorine-containing polymer (A) has 1,2 or 3 ether type oxygen atoms as ring-forming atoms, and when the fluorine-containing alicyclic ring contains a plurality of the ether type oxygen atoms, the ether type oxygen atoms are not adjacent to each other,
the content of the fluoropolymer (A) is 20% by mass or more based on the mass of the composition.
Item 2:
the composition according to claim 1, wherein the content of the fluoropolymer (A) is in the range of 20 to 65% by mass based on the mass of the composition.
Item 3:
the composition according to item 1 or 2, wherein the content of the fluoropolymer (A) is in the range of more than 20% by mass and not more than 65% by mass relative to the mass of the composition.
Item 4:
the composition according to any one of claims 1 to 3, wherein the aprotic solvent (B) is at least one solvent selected from the group consisting of a perfluoroaromatic compound, a perfluorotrialkylamine, a perfluoroalkane, a hydrofluorocarbon, a perfluorocyclic ether, a hydrofluoroether and an olefin compound containing at least one chlorine atom.
Item 5:
the composition according to any one of claims 1 to 4, wherein the aprotic solvent (B) is a hydrofluoroether.
Item 6:
the composition as described in any one of items 1 to 5, wherein the aprotic solvent (B) has a Global Warming Potential (GWP) of 400 or less.
Item 7:
the composition according to any one of claims 1 to 6, wherein the aprotic solvent (B) is selected from the group consisting of a compound represented by the formula (B-1), a compound represented by the formula (B-2), a compound represented by the formula (B-3), a compound represented by the formula (B-4), and (CF)3)2CHOCH3、(CF3)2CFOCH3、CF3CHFCF2OCH3And CF3CHFCF2OCF3At least one hydrofluoroether of (a).
F(CF2)pO(CH2)qH (B-1)
[ in the formula, p is an integer of 1 to 6, and q is an integer of 1 to 4. ]
H(CF2)pO(CF2)qF (B-2)
[ in the formula, p and q have the same meanings as described above. ]
H(CF2)pO(CH2)qH (B-3)
[ in the formula, p and q have the same meanings as described above. ]
X(CF2)pCH2O(CF2)qH (B-4)
[ in the formula, X represents a fluorine atom or a hydrogen atom, and p and q have the same meanings as described above. ]
Item 8:
the composition according to any one of claims 1 to 7, wherein the aprotic solvent (B) is a compound represented by the formula (B-5).
R21-O-R22 (B-5)
[ in the formula, R21Is a straight-chain or branched propyl or butyl group having one or more hydrogen atoms substituted by fluorine atoms, R22Is methyl or ethyl.]
Item 9:
the composition as described in any one of claims 1 to 8, wherein the fluorine-containing aliphatic ring of the fluorine-containing polymer (A) is a 4-, 5-, 6-or 7-membered ring.
Item 10:
the composition as described in any one of items 1 to 9, wherein the fluoropolymer (A) contains a structural unit represented by the following formula (A1), a structural unit represented by the following formula (A2), or a structural unit represented by the following formula (A3) as a main component.
Figure BDA0003627434700000031
[ in the formula, R1Represents a fluorine atom or a perfluoroalkyl group having C1 to C5.]
Figure BDA0003627434700000032
[ in the formula, R2～R5Each independently represents a fluorine atom, a perfluoroalkyl group having C1 to C5, or a perfluoroalkoxy group having C1 to C5.]
Figure BDA0003627434700000041
[ in the formula, R6～R9Each independently represents a fluorine atom, a perfluoroalkyl group having C1 to C5, or a perfluoroalkoxy group having C1 to C5.]
Item 11:
the composition according to any one of claims 1 to 10, wherein the fluoropolymer (A) contains a structural unit represented by the formula (A3) as a main component.
Item 12:
the composition according to any one of claims 1 and 4 to 8, wherein the fluoropolymer (A) is the fluoropolymer (A) other than a polymer containing a structural unit represented by the formula (A3) as a main component, and the content of the fluoropolymer (A) is 30% by mass or more based on the mass of the composition.
Item 13:
the composition according to item 12, wherein the content of the fluoropolymer (A) is more than 30% by mass based on the mass of the composition.
Item 14:
the composition as described in any one of items 1 to 10, wherein the fluoropolymer (A) contains a structural unit represented by the following formula (A1-1), a structural unit represented by the following formula (A2-1), a structural unit represented by the following formula (A2-2) or a structural unit represented by the following formula (A3-1) as a main component,
Figure BDA0003627434700000042
Figure BDA0003627434700000051
item 15:
the composition according to item 11, wherein the fluoropolymer (A) contains a structural unit represented by the formula (A3-1) as a main component.
Item 16:
the composition according to item 12 or 13, wherein the fluoropolymer (A) contains a structural unit represented by formula (A1-1), a structural unit represented by formula (A2-1) or a structural unit represented by formula (A2-2) as a main component.
Item 17:
the composition as described in any one of claims 1 to 16, wherein the fluoropolymer (A) has a mass average molecular weight of 5000 to 1000000.
Item 18:
the composition as described in any one of claims 1 to 17, wherein the fluoropolymer (A) has a mass average molecular weight of 40000 to 500000.
Item 19:
a process for producing a fluoropolymer (A) containing a structural unit having a fluorine-containing alicyclic ring as a main component, which comprises polymerizing a monomer in the presence of a polymerization initiator,
the fluorine-containing alicyclic ring of the fluorine-containing polymer (A) has 1,2 or 3 ether type oxygen atoms as ring-forming atoms, and when the fluorine-containing alicyclic ring contains a plurality of the ether type oxygen atoms, the ether type oxygen atoms are not adjacent to each other,
the monomer(s) include a monomer (M) corresponding to a structural unit contained as a main component in the fluoropolymer (A),
the above polymerization reaction is carried out in an aprotic solvent (B),
the aprotic solvent (B) is at least one solvent selected from the group consisting of a perfluoroaromatic compound, a perfluorotrialkylamine, a perfluoroalkane, a perfluorocyclic ether, a hydrofluoroether and an olefin compound containing at least one chlorine atom.
Item 20:
the production method according to claim 19, wherein the polymerization initiator has a half-life temperature of 10 hours in a range of 0 ℃ to 160 ℃, and the polymerization reaction is carried out in the aprotic solvent (B) under conditions of a temperature not higher than 20 ℃ higher than a boiling point lower than either of the monomer (M) and the aprotic solvent, and a temperature not higher than 20 ℃ higher than the 10-hour half-life temperature of the polymerization initiator.
Item 21:
the production method according to claim 19 or 20, wherein the polymerization initiator is a non-perfluorinated polymerization initiator.
Item 22:
the production method according to any one of claims 19 to 21, wherein the polymerization initiator is at least one selected from the group consisting of a compound represented by formula (C1), a compound represented by formula (C2), a compound represented by formula (C3), and an inorganic peroxide,
Figure BDA0003627434700000061
[ in the formula, R31And R32The same or different groups are those wherein at least one fluorine atom in a C3-C10 perfluoroalkyl group which may be substituted with a perfluorophenyl group is substituted with a hydrogen atom, and those wherein at least one fluorine atom in a perfluorophenyl group which may be substituted with a linear or branched C1-C4 perfluoroalkyl group is substituted with a hydrogen atom.]
Figure BDA0003627434700000062
[ in the formula, R33And R34The perfluoroalkyl groups may be identical or different and each have a hydrogen atom substituted for at least one fluorine atom in the C3-C10 perfluoroalkyl group which may be substituted with a perfluorophenyl group, or a hydrogen atom substituted for at least one fluorine atom in the perfluorophenyl group which may be substituted with a linear or branched C1-C4 perfluoroalkyl group.]
Figure BDA0003627434700000071
[ in the formula, R35And R36The perfluoroalkyl groups may be identical or different and each have a hydrogen atom substituted for at least one fluorine atom in the C1-C10 perfluoroalkyl group which may be substituted with a perfluorophenyl group, or a hydrogen atom substituted for at least one fluorine atom in the perfluorophenyl group which may be substituted with a linear or branched C1-C4 perfluoroalkyl group.]
Item 23:
the production method according to any one of claims 19 to 22, wherein the aprotic solvent (B) is a hydrofluoroether.
Item 24:
the production method according to any one of claims 19 to 23, wherein the aprotic solvent (B) has a Global Warming Potential (GWP) of 400 or less.
Item 25:
the production process according to any one of claims 19 to 24, wherein the aprotic solvent (B) is selected from the group consisting of a compound represented by the formula (B-1), a compound represented by the formula (B-2), a compound represented by the formula (B-3), a compound represented by the formula (B-4), and (CF)3)2CHOCH3、(CF3)2CFOCH3、CF3CHFCF2OCH3And CF3CHFCF2OCF3At least one hydrofluoroether of (a) at least one hydrofluoroether,
F(CF2)pO(CH2)qH (B-1)
[ in the formula, p is an integer of 1 to 6, and q is an integer of 1 to 4. ]
H(CF2)pO(CF2)qF (B-2)
[ in the formula, p and q have the same meanings as described above. ]
H(CF2)pO(CH2)qH (B-3)
[ in the formula, p and q have the same meanings as described above. ]
X(CF2)pCH2O(CF2)qH (B-4)
[ in the formula, X represents a fluorine atom or a hydrogen atom, and p and q have the same meanings as described above. ]
Item 26:
the production process according to any one of claims 19 to 25, wherein the aprotic solvent (B) is a compound represented by the formula (B-5),
R21-O-R22 (B-5)
[ in the formula, R21Is a straight-chain or branched propyl or butyl group having one or more hydrogen atoms substituted by fluorine atoms, R22Is methyl or ethyl.]
Item 27:
the production method according to any one of claims 19 to 26, wherein the amount of the aprotic solvent (B) in the polymerization reaction is in the range of 20 to 300 mass% based on the mass of the monomer (M).
Item 28:
the production method according to any one of claims 19 to 27, wherein the amount of the aprotic solvent (B) in the polymerization reaction is in the range of 50 to 200 mass% based on the mass of the monomer (M).
Item 29:
the production process according to any one of claims 19 to 28, wherein the fluorine-containing aliphatic ring of the fluorine-containing polymer (A) is a 4-, 5-, 6-or 7-membered ring.
Item 30:
the production method according to any one of claims 19 to 29, wherein the fluoropolymer (A) contains a structural unit represented by the following formula (A1), a structural unit represented by the following formula (A2), or a structural unit represented by the following formula (A3) as a main component,
Figure BDA0003627434700000081
[ in the formula, R1Represents a fluorine atom or a perfluoroalkyl group having C1 to C5.]
Figure BDA0003627434700000082
[ in the formula, R2～R5Each independently represents a fluorine atom, a perfluoroalkyl group having C1 to C5, or a perfluoroalkoxy group having C1 to C5.]
Figure BDA0003627434700000091
[ in the formula, R6～R9Independently represent a fluorine atom, a perfluoroalkyl group having C1 to C5 or a perfluoroalkoxy group having C1 to C5.]
Item 31:
the production method according to any one of claims 19 to 30, wherein the fluoropolymer (A) contains a structural unit represented by the formula (A3) as a main component.
Item 32:
the production method according to any one of claims 19 to 30, wherein the fluoropolymer (A) contains a fluoropolymer (A) other than a polymer containing a structural unit represented by the formula (A3) as a main component.
Item 33:
the production method according to any one of claims 19 to 30, wherein the fluoropolymer (A) contains a structural unit represented by the following formula (A1-1), a structural unit represented by the following formula (A2-1), a structural unit represented by the following formula (A2-2) or a structural unit represented by the following formula (A3-1) as a main component.
Figure BDA0003627434700000092
Figure BDA0003627434700000101
Item 34:
the production method according to item 31, wherein the fluoropolymer (A) contains a structural unit represented by formula (A3-1) as a main component.
Item 35:
the production process according to item 32, wherein the fluoropolymer (A) contains a structural unit represented by formula (A1-1), a structural unit represented by formula (A2-1), or a structural unit represented by formula (A2-2) as a main component.
Item 36:
the production method according to any one of claims 19 to 35, wherein the mass average molecular weight of the fluoropolymer (A) is in the range of 5000 to 1000000.
Item 37:
the production method according to any one of claims 19 to 36, wherein the mass average molecular weight of the fluoropolymer (A) is 40000 to 500000.
Item 38:
a composition comprising a fluorine-containing polymer (A) and an aprotic solvent (B), wherein the fluorine-containing polymer (A) contains a structural unit having a fluorine-containing aliphatic ring as a main component,
the fluoropolymer (A) contains a structural unit represented by the following formula (A3) as a main component,
Figure BDA0003627434700000102
[ in the formula, R6～R9Each independently represents a fluorine atom, a perfluoroalkyl group having C1 to C5, or a perfluoroalkoxy group having C1 to C5.]，
The aprotic solvent (B) is a non-perfluorinated solvent.
Item 39:
the composition according to item 38, wherein the non-perfluorinated solvent is a hydrofluoroether.
Item 40:
the composition according to item 38 or 39, wherein the non-perfluorinated solvent has a Global Warming Potential (GWP) of 400 or less.
Item 41:
the composition according to any one of claims 38 to 40, wherein the aprotic solvent (B) is selected from the group consisting of a compound represented by the formula (B-1), a compound represented by the formula (B-2), a compound represented by the formula (B-3), a compound represented by the formula (B-4), and (CF)3)2CHOCH3、(CF3)2CFOCH3、CF3CHFCF2OCH3And CF3CHFCF2OCF3At least one hydrofluoroether of (a).
F(CF2)pO(CH2)qH (B-1)
[ in the formula, p is an integer of 1 to 6, and q is an integer of 1 to 4. ]
H(CF2)pO(CF2)qF (B-2)
[ in the formula, p and q have the same meanings as described above. ]
H(CF2)pO(CH2)qH (B-3)
[ in the formula, p and q have the same meanings as described above. ]
X(CF2)pCH2O(CF2)qH (B-4)
[ in the formula, X represents a fluorine atom or a hydrogen atom, and p and q have the same meanings as described above. ]
Item 42:
the composition as described in any one of items 38 to 41, wherein the aprotic solvent is a compound represented by the formula (B-5).
R21-O-R22 (B-5)
[ wherein, R21Is a straight-chain or branched propyl or butyl group having one or more hydrogen atoms substituted by fluorine atoms, R22Is methyl or ethyl.]
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present disclosure, a method for producing a fluoropolymer containing a structural unit having a fluorinated alicyclic ring as a main component, which is soluble in an aprotic solvent at a high concentration (particularly, 20% by mass or more) can be provided. According to the present disclosure, a composition in which a fluoropolymer containing a structural unit having a fluorine-containing alicyclic ring as a main component is soluble at a high concentration (particularly, 20% by mass or more) in an aprotic solvent can be provided. According to the present disclosure, there can be provided a composition containing a fluoropolymer which is considered to be hardly soluble in a non-perfluorinated solvent and contains a structural unit represented by the formula (a3) as a main component, and a non-perfluorinated solvent, and in which the fluoropolymer is dissolved.
Detailed Description
The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure.
The ensuing description of the disclosure more particularly exemplifies illustrative embodiments.
In several portions of the present disclosure, guidance is provided through examples, and these examples can be used in various combinations.
In each case, the set of examples serves as a non-exclusive and representative set.
All publications, patents and patent applications cited in this specification are herein incorporated by reference as if fully set forth.
Term(s) for
The symbols and abbreviations in this specification, unless otherwise specified, may be understood as meaning commonly used in the art to which this disclosure belongs in the context of this specification.
In the present description, the term "comprising" is used in the meaning including the term "consisting essentially of … …" and the term "consisting of … …".
Unless otherwise specified, the procedures, treatments, or operations described in this specification may be performed at room temperature. In the present specification, room temperature may refer to a temperature within a range of 10 to 40 ℃.
In the present specification, the symbol "Cn-Cm" (where n and m each represent a number) represents a number of carbon atoms of n or more and m or less as generally understood by those skilled in the art.
In this specification, unless the skilled person specifies otherwise, compound labels include all stereoisomers (enantiomers, diastereomers, geometric isomers, etc.).
In the present specification, the term "compound represented by the formula (N)", the term "structural unit represented by the formula (N)", and the term "monomer represented by the formula (N)" may be referred to as a compound (N), a structural unit (N), and a monomer (N), respectively.
In the present specification, unless otherwise specified, "fluorine-containing alicyclic ring" means having a plurality of carbon atoms and 1,2 or 3 ether type oxygen atoms as ring-forming atoms. When the "fluorine-containing alicyclic ring" contains a plurality of oxygen atoms as ring-constituting atoms, the oxygen atoms are not adjacent to each other.
"fluoroaliphatic ring" includes saturated aliphatic monocyclic rings containing fluorine atoms.
The "fluorine-containing aliphatic ring" includes 4 or more rings (e.g., 4-membered ring, 5-membered ring, 6-membered ring, 7-membered ring).
The "fluorine-containing aliphatic ring" may have at least one substituent selected from a perfluoroalkyl group (for example, a linear or branched perfluoroalkyl group having C1 to C5) and a perfluoroalkoxy group (for example, a linear or branched perfluoroalkoxy group having C1 to C5), and the number of the substituents may be 1 or more, for example, 1 to 4, 1 to 3, 1 to 2, 1,2,3 or 4.
In the "fluorine-containing alicyclic ring", the ring-forming carbon atom may have a fluorine atom.
Examples of the "fluorine-containing alicyclic ring" include perfluorooxetane which may have 1 or more substituents, perfluorotetrahydrofuran which may have 1 or more substituents, perfluorodioxolane which may have 1 or more substituents, perfluorotetrahydropyran which may have 1 or more substituents, perfluoro-1, 3-dioxane which may have 1 or more substituents, perfluorohexylene oxide which may have 1 or more substituents, perfluoro-1, 3-dioxepane which may have 1 or more substituents, perfluoro-1, 4-dioxepane which may have 1 or more substituents, perfluoro-1, 3, 5-trioxepane which may have 1 or more substituents.
In the present specification, unless otherwise specified, examples of the "alkyl group" include straight-chain or branched-chain C1-C10 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl groups.
In the present specification, unless otherwise specified, "fluoroalkyl group" is an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The "fluoroalkyl group" may be a linear or branched fluoroalkyl group.
The "fluoroalkyl group" may have, for example, 1 to 12 carbon atoms, 1 to 6 carbon atoms, 1 to 5 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, 6 carbon atoms, 5 carbon atoms, 4 carbon atoms, 3 carbon atoms, 2 carbon atoms or 1 carbon atom.
The number of fluorine atoms in the "fluoroalkyl group" may be 1 or more (for example, 1 to 3, 1 to 5, 1 to 9, 1 to 11, or from 1 to the maximum number that can be substituted).
"fluoroalkyl" includes perfluoroalkyl. "perfluoroalkyl" is a group in which all of the hydrogen atoms in the alkyl group have been replaced with fluorine atoms.
Examples of perfluoroalkyl groups include trifluoromethyl (CF)3-) pentafluoroethyl (C)2F5-), heptafluoropropyl (CF)3CF2CF2-) and heptafluoroisopropyl ((CF)3)2CF-)。
Specific examples of the "fluoroalkyl group" include a monofluoromethyl group, a difluoromethyl group, and a trifluoromethyl group (CF)3-), 2,2, 2-trifluoroethyl, perfluoroethyl (C)2F5-), tetrafluoropropyl (e.g. HCF)2CF2CH2-), hexafluoropropyl (e.g. (CF)3)2CH-), perfluorobutyl (e.g. CF)3CF2CF2CF2-), octafluoropentyl radical (e.g. HCF)2CF2CF2CF2CH2-), perfluoropentyl (e.g. CF)3CF2CF2CF2CF2-) and perfluorohexyl (e.g. CF3CF2CF2CF2CF2CF2-) and the like.
In this specification, unless otherwise specified, "alkoxy" may be represented by RO- [ wherein R is an alkyl group (e.g., C1-C10 alkyl). A group represented by.
Examples of the "alkoxy group" include linear or branched alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, and decyloxy.
In the present specification, unless otherwise specified, "fluoroalkoxy" is an alkoxy group in which at least one hydrogen atom is substituted with a fluorine atom. The "fluoroalkoxy group" may be a linear or branched fluoroalkoxy group.
The "fluoroalkoxy group" has 1 to 12 carbon atoms, 1 to 6 carbon atoms, 1 to 5 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, 6 carbon atoms, 5 carbon atoms, 4 carbon atoms, 3 carbon atoms, 2 carbon atoms or 1 carbon atom, for example.
The number of fluorine atoms contained in the "fluoroalkoxy group" may be 1 or more (e.g., 1 to 3, 1 to 5, 1 to 9, 1 to 11, 1 to the maximum number that can be substituted).
"fluoroalkoxy" includes perfluoroalkoxy. "perfluoroalkoxy" is a group in which all of the hydrogen atoms in the alkoxy group have been replaced with fluorine atoms.
Examples of "perfluoroalkoxy" include trifluoromethoxy, pentafluoroethoxy, heptafluoropropoxy, and heptafluoroisopropoxy.
Specific examples of the "fluoroalkoxy group" include fluoromethoxy, difluoromethoxy, trifluoromethoxy, pentafluoroethoxy and heptafluoropropoxy (e.g., CF)3CF2CF2O-、(CF3)2CFO-) and nonafluorobutoxy (e.g., CF)3CF2CF2CF2O-、(CF3)3CO-) and the like.
Composition comprising a metal oxide and a metal oxide
One embodiment of the present disclosure is a composition containing a fluoropolymer (a) having a structural unit having a fluorine-containing alicyclic ring as a main component and an aprotic solvent (B). The composition is preferably in a liquid state, and the fluoropolymer (A) is dissolved therein.
In the composition, the fluorine-containing aliphatic ring of the fluorine-containing polymer (A) has 1,2 or 3 ether type oxygen atoms as ring-forming atoms, and when the fluorine-containing aliphatic ring contains a plurality of the ether type oxygen atoms, the ether type oxygen atoms are not adjacent to each other.
Fluorine-containing Polymer (A)
The fluorine-containing polymer (A) contains a structural unit having a fluorine-containing alicyclic ring as a main component. The phrase "containing a structural unit as a main component" means that the proportion of the structural unit to all the structural units in the fluoropolymer (a) is 50 mol% or more.
The proportion of the structural unit having a fluorine-containing alicyclic ring in the fluoropolymer (a) is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 100 mol%.
The kind of the structural unit having a fluorine-containing aliphatic ring in the fluorine-containing polymer (a) may be 1 or more, preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.
The structural unit having a fluorine-containing aliphatic ring has 1,2 or 3 ether type oxygen atoms as ring-forming atoms, and when the fluorine-containing aliphatic ring contains a plurality of ether type oxygen atoms, the ether type oxygen atoms are not adjacent to each other.
The fluorine-containing alicyclic ring contains two or more (e.g., 2,3, 4) carbon atoms as ring-forming atoms, and the carbon-carbon bond formed between adjacent carbon atoms may contain 1 or more (e.g., 1,2,3, 4,5, 6).
The fluorine-containing alicyclic ring contains, as ring-forming atoms, 2 or more carbon atoms and 1,2 or 3 oxygen atoms, and preferably contains no other atoms.
The fluorine-containing alicyclic ring preferably does not contain a hydrogen atom.
The fluorine-containing alicyclic ring is preferably an alicyclic ring in which all hydrogen atoms are substituted by fluorine atoms.
The fluorine-containing aliphatic ring may be a 4-membered ring, a 5-membered ring, a 6-membered ring or a 7-membered ring. From the viewpoint of various physical properties of the fluoropolymer (a), the fluorine-containing aliphatic ring is preferably a 4-membered ring, a 5-membered ring or a 6-membered ring, and more preferably a 5-membered ring.
The fluorine-containing aliphatic 4-membered ring may contain 3 carbon atoms and 1 oxygen atom as ring-constituting atoms. Examples of the fluorine-containing aliphatic 4-membered ring include perfluorooxetane. As the ring-forming atoms, the fluorine-containing aliphatic 5-membered ring may contain 4 carbon atoms and 1 oxygen atom, or 3 carbon atoms and 2 oxygen atoms. Examples of the fluorine-containing aliphatic 5-membered ring include a perfluorotetrahydrofuran ring and a perfluorodioxolane ring.
As the ring-forming atoms, the fluorine-containing aliphatic 6-membered ring may contain 5 carbon atoms and 1 oxygen atom, or may also contain 4 carbon atoms and 2 oxygen atoms. Examples of the fluorine-containing aliphatic 6-membered ring include a perfluorotetrahydropyrane ring and a perfluoro-1, 3-dioxane.
The fluoroaliphatic 7-membered ring can contain, as ring-forming atoms, 6 carbon atoms and 1 oxygen atom, and can also contain 5 carbon atoms and 2 oxygen atoms, and can also contain 4 carbon atoms and 3 oxygen atoms. Examples of the fluorine-containing aliphatic 7-membered ring include perfluoroepoxyhexane, perfluoro-1, 3-dioxepane, perfluoro-1, 4-dioxepane and perfluoro-1, 3, 5-trioxepane.
The fluorine-containing alicyclic ring may have 1 or more substituents. When there are plural substituents, they may be the same or different.
The substituent may be at least 1 selected from a perfluoroalkyl group (for example, a linear or branched perfluoroalkyl group having from C1 to C5) and a perfluoroalkoxy group (for example, a linear or branched perfluoroalkoxy group having from C1 to C5). The number of the substituent may be 1 or more, for example, 1 to 4, 1 to 3, 1 to 2, 1,2,3, 4.
The substituent is preferably at least one group selected from the group consisting of trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, trifluoromethoxy, and perfluoroethoxy, more preferably at least one group selected from the group consisting of trifluoromethyl, perfluoroethyl, perfluoropropyl, and perfluoroisopropyl, and particularly preferably at least one group selected from the group consisting of trifluoromethyl, perfluoroethyl, and trifluoromethoxy.
The structural unit having a fluorine-containing alicyclic ring may have 1 or 2 perfluoroalkylene groups in addition to the fluorine-containing alicyclic ring. The perfluoroalkylene group is bonded to the ring-forming carbon atom of the fluorine-containing aliphatic ring to form the main chain of the fluorine-containing polymer (A).
An example of such a perfluoroalkylene group is two-CF groups other than the perfluoromethylene group constituting the ring in the structural unit represented by the following formula (A1-1)2-. The perfluoroalkylene group in the structural unit may be 1. When 2 perfluoroalkylene groups are contained, they may be the same or different.
Figure BDA0003627434700000161
An example of perfluoroalkylene is- (CF)2)nAn alkylene group represented by the formula, wherein n represents an integer of 1 to 4.
The perfluoroalkylene group contained in the structural unit having a fluorine-containing aliphatic ring may have 1 or more perfluoroalkyl groups as a substituent. When the substituent is plural, the substituents may be the same or different. The number of the substituent may be 1 or more, for example, 1 to 4, 1 to 3, 1 to 2, 1,2,3 or 4.
The substituent is preferably at least 1 group selected from the group consisting of a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group and a heptafluoroisopropyl group, and more preferably at least 1 group selected from the group consisting of a trifluoromethyl group and a pentafluoroethyl group.
The structural unit having a fluorine-containing alicyclic ring may be a structural unit represented by any one of the following formulae (a1) to (A3) (also referred to as "structural unit (a 1)", "structural unit (a 2)" and "structural unit (A3)", respectively, in the present specification). The structural units (a1), (a2) and (A3) may be 1 kind or a combination of two or more kinds alone.
Figure BDA0003627434700000171
[ in the formula, R1Represents a fluorine atom or a perfluoroalkyl group having C1 to C5.]
Figure BDA0003627434700000172
[ in the formula, R2～R5Each independently represents a fluorine atom, a perfluoroalkyl group having C1 to C5, or a perfluoroalkoxy group having C1 to C5.]
Figure BDA0003627434700000173
[ in the formula, R6～R9Independently represent a fluorine atom, a perfluoroalkyl group having C1 to C5 or a perfluoroalkoxy group having C1 to C5.]
In the structural unit (A1), R1May be a fluorine atom or a linear or branched C1-C4A branched perfluoroalkyl group. R1Preferably a fluorine atom, a trifluoromethyl group or a perfluoroethyl group, more preferably a fluorine atom or a trifluoromethyl group, and particularly preferably a fluorine atom.
Preferred examples of the structural unit (A1) include a structural unit represented by the following formula (A1-1), (also referred to as "structural unit (A1-1)" in the specification).
Figure BDA0003627434700000174
In the structural unit (A2), R2～R5Independently of one another, the fluorine atom, a linear or branched perfluoroalkyl group having from C1 to C3, or a linear or branched perfluoroalkoxy group having from C1 to C3 may be mentioned. R2～R5Each independently, preferably a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group or a trifluoromethoxy group, and more preferably a fluorine atom, a trifluoromethyl group or a trifluoromethoxy group.
A preferred structural unit (A2) is R in the formula (A2)2And R3Each independently represents a fluorine atom, a trifluoromethyl group or a trifluoromethoxy group, R4And R5Each independently represents a fluorine atom or a structural unit of a trifluoromethyl group.
A more preferred structural unit (A2) is R in the formula (A2)2Represents a fluorine atom, R3Represents a fluorine atom, trifluoromethyl or trifluoromethoxy, R4And R5Each independently represents a fluorine atom or a structural unit of a trifluoromethyl group.
A particularly preferred structural unit (A2) is R in the formula (A2)2Represents a fluorine atom, R3Represents a fluorine atom or a trifluoromethoxy group, R4And R5The same indicates a fluorine atom or a structural unit of a trifluoromethyl group.
Preferred examples of the structural unit (A2) include structural units represented by the following formula (in the present specification, referred to as "structural unit (A2-1)" and "structural unit (A2-2)").
Figure BDA0003627434700000181
In the structural unit (A3), R6～R9Independently of one another, the fluorine atom, a linear or branched perfluoroalkyl group having from C1 to C3, or a linear or branched perfluoroalkoxy group having from C1 to C3 may be mentioned. R6～R9Each independently, preferably a fluorine atom, a trifluoromethyl group, a perfluoroethyl group or a trifluoromethoxy group, more preferably a fluorine atom, a trifluoromethyl group or a trifluoromethoxy group.
A preferred structural unit (A3) is R in the formula (A3)6～R9Each independently represents a fluorine atom or a structural unit of a trifluoromethyl group.
A more preferred structural unit (A3) is in the formula (A3),
R6～R9represents a fluorine atom,
R6～R8Represents a fluorine atom, R9Represents a trifluoromethyl group, and represents a trifluoromethyl group,
R6represents trifluoromethyl, R7～R9Represents a fluorine atom, and is represented by,
or R6～R9Represents trifluoromethyl, R7And R8Represents a structural unit of a fluorine atom.
Preferred examples of the structural unit (A3) include a structural unit represented by the following formula (also referred to as "structural unit (A3-1)" in the present specification).
Figure BDA0003627434700000191
The fluoropolymer (a) may contain other structural units in addition to the structural unit having a fluorine-containing alicyclic ring contained as a main component. The proportion of the other structural unit in all the structural units in the fluoropolymer (a) may be 50 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less, and particularly preferably 0 mol%.
Examples of the other structural unit include a structural unit represented by the following formula (a11) (also referred to as "structural unit (a 11)" in the present specification), but are not limited thereto.
Figure BDA0003627434700000192
[ in the formula, R111Represents a fluorine atom, a perfluoroalkyl group having C1 to C6, or a perfluoroalkoxy group having C1 to C6.]
For example, the fluoropolymer (A) may contain a structural unit (A2-1) and a structural unit represented by the following formula (A11-1) (also referred to as "structural unit (A11-1)" in the present specification).
Figure BDA0003627434700000193
R111May be a fluorine atom, a linear or branched perfluoroalkyl group having from C1 to C6, or a linear or branched perfluoroalkoxy group having from C1 to C6.
Preferred R111Is a fluorine atom, a linear or branched C1-C4 perfluoroalkyl group or a linear or branched C1-C4 perfluoroalkoxy group.
More preferred R111Is a fluorine atom, a linear or branched C1-C3 perfluoroalkyl group or a linear or branched C1-C3 perfluoroalkoxy group.
Particularly preferred R111Is a fluorine atom or a trifluoroalkyl group.
The mass average molecular weight of the fluoropolymer (A) may be, for example, 5000 to 1000000, 10000 to 500000, 90000 to 350000, or the like, preferably 10000 to 750000, more preferably 40000 to 500000, and particularly preferably 70000 to 350000.
The lower limit of the mass average molecular weight of the fluoropolymer (a) may be, for example, 5000 or more, preferably 10000 or more, more preferably 40000 or more, and particularly preferably 70000 or more. The upper limit of the mass average molecular weight of the fluoropolymer (a) may be, for example, 1000000 or less, preferably 750000 or less, more preferably 500000 or less, and particularly preferably 350000 or less. The above lower and upper limits may be appropriately combined.
The mass average molecular weight of the fluoropolymer (a) is a value determined by GPC (gel permeation chromatography), particularly the GPC described in the examples.
In the composition of the present disclosure, the content of the fluoropolymer (a) may be 20% by mass or more with respect to the mass of the composition. Preferably in the range of 20 mass% to 65 mass%, more preferably in the range of more than 20 mass% and 65 mass% below, and particularly preferably in the range of more than 20 mass% and 50 mass% below.
The fluoropolymer (a) other than the polymer containing the structural unit (A3) as a main component means a polymer other than the polymer containing the structural unit (A3) as a main component in the fluoropolymer (a). In other words, the above-mentioned fluoropolymer (a) other than the polymer containing the structural unit (A3) as a main component means a fluoropolymer (a) containing, as a main component, a structural unit having a fluorine-containing alicyclic ring having 1,2 or 3 ether-type oxygen atoms as ring-forming atoms, and when the fluorine-containing alicyclic ring contains a plurality of the ether-type oxygen atoms, the ether-type oxygen atoms are not adjacent to each other but belong to the fluoropolymer (a), but do not belong to the polymer containing the structural unit (A3) as a main component.
The fluoropolymer (a) can be synthesized by a known method. For example, it can be synthesized by polymerizing a monomer corresponding to the structural unit of the fluoropolymer. As the polymerization method, radical polymerization, bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, or the like can be used. The method for producing the fluoropolymer (a) of the present disclosure is particularly preferable because the fluoropolymer (a) can be dissolved in a solvent at a high concentration.
Aprotic solvent (B)
The composition of the present disclosure contains an aprotic solvent (B). The aprotic solvent includes at least one solvent selected from the group consisting of a perfluorinated solvent and a non-perfluorinated solvent.
The perfluoro solvent is a solvent containing a fluorine atom and a carbon atom but not a hydrogen atom in an aprotic solvent. Examples of the perfluoro solvent include a perfluoroaromatic compound, a perfluorotrialkylamine, a perfluoroalkane, and a perfluorocyclic ether. The perfluorosolvent may be used alone in 1 kind or in combination of 2 or more kinds.
The non-perfluorinated solvent is a solvent containing a fluorine atom, a carbon atom and a hydrogen atom in the aprotic solvent. Examples of the non-perfluorinated solvent include hydrofluorocarbons, hydrofluoroethers, and olefin compounds containing at least one chlorine atom. The non-perfluorinated solvents may be used alone or in combination of two or more. Since global warming potential is generally lower than that of perfluorinated solvents, non-perfluorinated solvents are preferred solvents from the viewpoint of environmental load. On the other hand, the non-perfluorinated solvent is considered to have a low performance of dissolving the fluoropolymer, but the inventors of the present invention found that it can dissolve the polymer containing the structural unit (A3) as a main component.
The perfluoroaromatic compound is, for example, a perfluoroaromatic compound which may have 1 or more perfluoroalkyl groups. The aromatic ring of the perfluoroaromatic compound may be at least one ring selected from a benzene ring, a naphthalene ring and an anthracene ring. The perfluoroaromatic compound may have 1 or more (e.g., 1,2,3 aromatic rings).
The perfluoroalkyl group as a substituent is, for example, a linear or branched perfluoroalkyl group having from C1 to C6, from C1 to C5 or from C1 to C4, preferably a linear or branched perfluoroalkyl group having from C1 to C3, more preferably a trifluoromethyl group or a pentafluoroethyl group.
The number of the substituent is, for example, 1 to 4, preferably 1 to 3, and more preferably 1 to 2. When there are plural substituents, they may be the same or different.
Examples of the perfluoroaromatic compound include perfluorobenzene, perfluorotoluene, perfluoroxylene, perfluoronaphthalene.
Preferred examples of the perfluoroaromatic compound include perfluorobenzene and perfluorotoluene.
The perfluorotrialkylamine is, for example, an amine substituted with 3 linear or branched perfluoroalkyl groups. The perfluoroalkyl group has, for example, 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and more preferably 1 to 4 carbon atoms. The perfluoroalkyl groups are identical or different, preferably identical.
Examples of the perfluorotrialkylamine include perfluorotrimethylamine, perfluorotriethylamine, perfluorotripropylamine, perfluorotriisopropylamine, perfluorotributylamine, perfluorotri-tert-butylamine, perfluorotripentylamine, perfluorotriisopentylamine, and perfluorotripentanylamine.
Preferred examples of the perfluorotrialkylamine include perfluorotripropylamine and perfluorotributylamine.
The perfluoroalkane is, for example, a linear, branched or cyclic perfluoroalkane having from C3 to C12 (preferably from C3 to C10, more preferably from C3 to C6).
Examples of perfluoroalkanes include perfluoropentane, perfluoro-2-methylpentane, perfluorohexane, perfluoro-2-methylhexane, perfluoroheptane, perfluorooctane, perfluorononane, perfluorodecane, perfluorocyclohexane, perfluoro (methylcyclohexane), perfluoro (dimethylcyclohexane) (e.g., perfluoro (1, 3-dimethylcyclohexane)), perfluorodecalin.
Preferred examples of the perfluoroalkanes include perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane.
The hydrofluorocarbons are, for example, C3 to C8 hydrofluorocarbons. Examples of hydrofluorocarbons include CF3CH2CF2H、CF3CH2CF2CH3、CF3CHFCHFC2F51,1,2,2,3,3, 4-heptafluorocyclopentane, CF3CF2CF2CF2CH2CH3、CF3CF2CF2CF2CHF2And CF3CF2CF2CF2CF2CH2CH3。
Preferred examples of hydrofluorocarbons include CF3CH2CF2H、CF3CH2CF2CH3。
The perfluorocyclic ether is, for example, a perfluorocyclic ether which may have 1 or more perfluoroalkyl groups. The ring of the perfluorocyclic ether may be a 3-to 6-membered ring. The perfluoro cyclic ether may have a ring having 1 or more oxygen atoms as ring-constituting atoms. The ring preferably has 1 or 2, more preferably 1, oxygen atoms.
Examples of the perfluoroalkyl group as a substituent include linear or branched perfluoroalkyl groups having from C1 to C6, from C1 to C5, and from C1 to C4. The perfluoroalkyl group is preferably a linear or branched perfluoroalkyl group having 1 to 3 carbon atoms.
The number of the substituent is, for example, 1 to 4, preferably 1 to 3, and more preferably 1 to 2. When there are plural substituents, they may be the same or different.
Examples of the perfluoro cyclic ether include perfluoro tetrahydrofuran, perfluoro-5-methyltetrahydrofuran, perfluoro-5-ethyltetrahydrofuran, perfluoro-5-propyltetrahydrofuran, perfluoro-5-butyltetrahydrofuran, perfluorotetrahydropyran.
Preferred examples of the perfluoro cyclic ether include perfluoro-5-ethyltetrahydrofuran, perfluoro-5-butyltetrahydrofuran.
The hydrofluoroether is, for example, a fluorine-containing ether.
The hydrofluoroether preferably has a Global Warming Potential (GWP) of 600 or less, more preferably 400 or less, and even more preferably 300 or less. The lower limit of the Global Warming Potential (GWP) of the hydrofluoroether may be 1 or more, or may be 5 or more.
Examples of hydrofluoroethers include CF3CF2CF2CF2OCH3、CF3CF2CF(CF3)OCH3、CF3CF(CF3)CF2OCH3、CF3CF2CF2CF2OC2H5、CF3CH2OCF2CHF2、C2F5CF(OCH3)C3F7、(CF3)2CHOCH3、(CF3)2CFOCH3、CHF2CF2OCH2CF3、CHF2CF2CH2OCF2CHF2、CF3CHFCF2OCH3、CF3CHFCF2OCF3Trifluoromethyl 1,2,2, 2-tetrafluoroethyl ether (HFE-227me), difluoromethyl 1,1,2,2, 2-pentafluoroethyl ether (HFE-227mc), trifluoromethyl 1,1,2, 2-tetrafluoroethyl ether (HFE-227pc), difluoromethyl 2,2, 2-trifluoroethyl ether (HFE-245mf), 2, 2-difluoroethyltrifluoromethyl ether (HFE-245pf), 1,1,2,3, 3-hexafluoropropyl methyl ether (CF3CHFCF2OCH3), 1,1,1,2, 2-tetrafluoroethyl 2,2, 2-trifluoroethyl ether (HFE-227me), 1,1,2, 2-tetrafluoroethyl ether (CF 3-CHFCF 2OCH3), 2, 2-trifluoroethyl ether (HFE-227mc)(CHF2CF2OCH2CF3) And 1,1,1,3,3, 3-hexafluoro-2-methoxypropane ((CF)3)2CHOCH3)。
Preferred examples of hydrofluoroethers include CF3CF2CF2CF2OCH3、CF3CF2CF2CF2OC2H5、CF3CH2OCF2CHF2、C2F5CF(OCH3)C3F71,1,2,3, 3-hexafluoropropyl methyl ether (CF)3CHFCF2OCH3)1, 1,1,2, 2-tetrafluoroethyl, 2,2, 2-trifluoroethyl ether (CHF)2CF2OCH2CF3) And 1,1,1,3,3, 3-hexafluoro-2-methoxypropane ((CF)3)2CHOCH3)。
The hydrofluoroether may be selected from the group consisting of compounds represented by the following formula (B-1), compounds represented by the following formula (B-2), compounds represented by the following formula (B-3), compounds represented by the following formula (B-4), and (CF)3)2CHOCH3、(CF3)2CFOCH3、CF3CHFCF2OCH3And CF3CHFCF2OCF3At least 1 kind of (1).
Formula (B-1):
F(CF2)pO(CH2)qH (B-1)
[ in the formula, p is an integer of 1 to 6, and q is an integer of 1 to 4. ]
Formula (B-2):
H(CF2)pO(CF2)qF (B-2)
[ in the formula, p and q have the same meanings as described above. ]
Formula (B-3):
H(CF2)pO(CH2)qH (B-3)
[ in the formula, p and q have the same meanings as described above. ]
Formula (B-4):
X(CF2)pCH2O(CF2)qH(B-4)
[ in the formula, X represents a fluorine atom or a hydrogen atom, and p and q have the same meanings as described above. ]
The hydrofluoroether is more preferably a compound represented by the following formula (B-5),
R21-O-R22 (B-5)
[ in the formula, R21Is a linear or branched propyl or butyl group having 1 or more hydrogen atoms substituted with fluorine atoms, R22Is methyl or ethyl.]
The compound represented by the formula (B-5) may be R21Is perfluorobutyl, R22A compound that is methyl or ethyl.
The olefin compound containing at least one chlorine atom is a C2-C4 (preferably C2-C3) olefin compound containing at least one chlorine atom in its structure. The olefin compound containing at least one chlorine atom is a compound in which at least 1 hydrogen atom bonded to a carbon atom is substituted with a chlorine atom in a hydrocarbon having 2 to 4 carbon atoms and 1 or 2 (preferably 1) double bonds.
The number of chlorine atoms is from 1 to the maximum number which can be substituted. The number of chlorine atoms may be, for example, 1,2,3, 4,5, etc.
The olefinic compound containing at least one chlorine atom can contain at least 1 (e.g., 1,2,3, 4,5, etc.) fluorine atom.
Examples of the olefin compound containing at least one chlorine atom include CH2＝CHCl、CHCl＝CHCl、CCl2＝CHCl、CCl2＝CCl2、CF3CH＝CHCl、CHF2CF＝CHCl、CFH2CF＝CHCl、CF3CCl＝CFCl、CF2HCl＝CFCl、CFH2Cl＝CFCl。
Preferred examples of olefinic compounds containing at least one chlorine atom include CHCl ═ CHCl, CHF2CF＝CHCl、CF3CH＝CHCl、CF3CCl＝CFCl。
The aprotic solvent (B) is preferably hydrofluoroether because it has little influence on the environment when used and is easily distilled off from the polymer.
The aprotic solvent (B) may have a Global Warming Potential (GWP) of 600 or less, 400 or less, or the like, preferably 375 or less, more preferably 350 or less, and particularly preferably 0. The lower limit of the Global Warming Potential (GWP) of the aprotic solvent (B) may be 1 or more, or may be 5 or more.
In the composition of the present disclosure, the content of the aprotic solvent (B) with respect to the mass of the above composition may be set to 80 mass% or less. Preferably 35 to 80% by mass, more preferably 35 to 80% by mass, and particularly preferably 50 to 80% by mass.
Other ingredients
The composition of the present disclosure may contain a raw material monomer, an oligomer formed from the raw material monomer, a polymerization initiator, impurities derived from the raw material, and the like, in addition to the fluoropolymer (a) and the aprotic solvent (B). The amounts of the above-mentioned respective components contained in the composition can be adjusted by setting, for example, the production conditions of the fluoropolymer (a), such as temperature, time, the kind and amount of raw material monomers, the kind and amount of solvent, the kind and amount of polymerization initiator, and the like. The amounts of the respective components can be adjusted by purification after the production of the fluoropolymer (A).
Composition (A3) comprising fluoropolymer (A3) and aprotic solvent (B)
The "fluoropolymer (A3)" is an embodiment of the fluoropolymer (a) and means a fluoropolymer (a) containing the structural unit (A3) as a main component.
The "composition (A3)" is one embodiment of the composition of the present disclosure described so far, and is a composition containing the fluoropolymer (a) having the structural unit (A3) as a main component and the aprotic solvent (B).
A composition (A3) containing the fluoropolymer (A3) and the aprotic solvent (B) is an embodiment of the composition of the present disclosure. Therefore, the composition (a3) can be applied not only to the matters described so far but also to substitutes for the matters described before or in addition to the matters described in this section.
In the composition (A3), the content of the fluoropolymer (A3) may be, for example, 20 mass% or more, 30 mass% or more, more than 30 mass%, 31 mass% or more, preferably in the range of 20 mass% to 65 mass%, in the range of more than 20 mass% to 65 mass%, in the range of 20 mass% to 50 mass%, more preferably in the range of 30 mass% to 65 mass%, in the range of more than 30 mass% to 65 mass%, in the range of 31 mass% to 65 mass%, particularly preferably in the range of 30 mass% to 50 mass%, in the range of more than 30 mass% to 50 mass%, or in the range of 31 mass% to 50 mass%.
In the composition (a3), the content of the aprotic solvent may be, for example, 80 mass% or less, 70 mass% or less, less than 70 mass%, or 69 mass% or less, preferably in the range of 35 to 80 mass%, or in the range of 50 to 80 mass%, more preferably in the range of 35 to 70 mass%, or in the range of 35 to 69 mass%, particularly preferably in the range of 50 to 70 mass%, or in the range of 50 to 69 mass%.
Composition (A3-2) comprising a fluoropolymer (A3) and a non-perfluorinated solvent as the aprotic solvent (B)
Another aspect of the composition of the present disclosure is a composition (A3-2) containing the fluoropolymer (A3) and a non-perfluorinated solvent as the aprotic solvent (B). The fluoropolymer (A3) in the composition (A3-2) may be dissolved in any solvent, whether or not the solvent is a non-perfluorinated solvent.
For the composition (A3-2), the concentration of the fluoropolymer (A3) may be less than 20% by mass, to which the description is applicable.
Method for producing fluoropolymer (A)
The fluoropolymer (a) is produced by polymerizing monomers in the presence of a polymerization initiator.
The above-mentioned monomer includes a monomer (M) corresponding to a structural unit contained in the fluoropolymer (a) as a main component.
The polymerization reaction is carried out in an aprotic solvent (B).
The aprotic solvent (B) is at least one solvent selected from the group consisting of a perfluoroaromatic compound, a perfluorotrialkylamine, a perfluoroalkane, a perfluorocyclic ether, a hydrofluoroether and an olefin compound containing at least 1 chlorine atom.
In the process for producing the fluoropolymer (a) of the present disclosure, the aprotic solvent (B) having a high content or dissolution amount of the fluoropolymer (a) is obtained. Therefore, the production method of the present disclosure is suitable as a method for producing the composition of the present disclosure.
Monomer
The "monomer (M)" is a monomer corresponding to a structural unit contained as a main component in the fluoropolymer (A). As the monomer, other monomers than the monomer (M) may be used. In the present specification, a monomer having a structural unit contained in the fluoropolymer (a) and corresponding to a structural unit other than the structural unit contained as a main component may be referred to as "other monomer".
It is understood by those skilled in the art that the fluoropolymer (A) having a structural unit corresponding to the monomer (A) is obtained by polymerizing a specific monomer. Accordingly, the person skilled in the art can select suitable monomers for the production of the desired fluoropolymer (a).
For example, the monomers corresponding to the structural unit (A1-1), the structural unit (A2-1), the structural unit (A2-2), the structural unit (A3-1) and the structural unit (A11-1) are monomers represented by the following formulae (M1-1), the formula (M2-1), the formula (M2-2), the formula (M3-1) and the formula (M11-1), and may be referred to as "monomer (M1-1)", "monomer (M2-1)", "monomer (M2-2)", "monomer (M3-1)" and "monomer (M11-1)", respectively, in the present specification.
Figure BDA0003627434700000261
The monomer (M) may be used alone in 1 kind or in combination of 2 or more kinds. Further, the monomer (M) may be used in combination with other monomers. For example, by combining the monomer (A2-1) and the monomer (A11-1), the fluoropolymer (A) containing the structural unit (A2-1) and the structural unit (A11-1) can be produced.
Aprotic solvent (B)
In the production method of the present disclosure, the monomer is polymerized in the aprotic solvent (B). For details of the aprotic solvent (B), reference will be made to the description of the aprotic solvent (B) in the composition of the present disclosure, unless otherwise specified.
Polymerization initiator
In the production method of the present disclosure, the monomer is subjected to a polymerization reaction in the presence of a polymerization initiator. The polymerization initiator may be any polymerization initiator as long as it can polymerize the monomer (M). The polymerization initiator preferably has a 10 hour half-life temperature in the range of 0 ℃ to 160 ℃.
The polymerization initiator preferably contains a fluorine atom because a liquid composition having a high content of the fluorine-containing polymer (A) can be obtained. The polymerization initiator is more preferably a non-perfluorinated polymerization initiator. The non-perfluorinated polymerization initiator is a polymerization initiator containing a hydrogen atom and a fluorine atom. Thus, the non-perfluorinated polymerization initiator does not include perfluorinated compounds.
The polymerization initiator may be used singly or in combination of 2 or more.
Examples of the polymerization initiator include compounds represented by the following formulae (C1), (C2), and (C3) and inorganic peroxides, and are referred to as "compound (C1)", "compound (C2)", and "compound (C3)", respectively, in the present specification. The compounds (C1) to (C3) and the inorganic peroxide may be used alone or in combination of 1.
Figure BDA0003627434700000271
[ in the formula, R31And R32Identical or different from each other, is a perfluoroalkyl group of C3-C10 which may be substituted by a perfluorophenyl groupA group in which at least one fluorine atom is substituted with a hydrogen atom, and a group in which at least 1 fluorine atom is substituted with a hydrogen atom in a perfluorophenyl group which may be substituted with a linear or branched perfluoroalkyl group having C1 to C4.]
Figure BDA0003627434700000281
[ in the formula, R33And R34The same or different groups are those wherein at least 1 fluorine atom in the C3-C10 perfluoroalkyl group which may be substituted with a perfluorophenyl group is substituted with a hydrogen atom, and those wherein at least 1 fluorine atom in the perfluorophenyl group which may be substituted with a linear or branched C1-C4 perfluoroalkyl group is substituted with a hydrogen atom.]
Formula (C3):
Figure BDA0003627434700000282
[ in the formula, R35And R36The perfluoroalkyl group may be a perfluoroalkyl group having 1 to 10, which may be substituted with a perfluorophenyl group, in which at least one fluorine atom is replaced with a hydrogen atom, or a perfluoroalkyl group having 1 to 4, which may be linear or branched, in which at least 1 fluorine atom is replaced with a hydrogen atom.]
R31And R32Preferably the same or different, perfluoropropyl group, perfluoroisopropyl group, perfluoro 2-phenyl-2-propyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluoro tert-butyl group, perfluoropentyl group, perfluoroisopentyl group, perfluoro neopentyl group, perfluoro 2-methyl-2-pentyl group, perfluoro 2,4, 4-trimethyl-2-pentyl group, perfluorohexyl group, perfluoro 2-methylhexyl group, perfluoro 2-ethylhexyl group, perfluorocyclohexyl group, perfluoro 4-methylcyclohexyl group, perfluoro 4-ethylcyclohexyl group, perfluoro 4-tert-butylcyclohexyl group, perfluoroheptyl group, perfluoro 2-heptyl group, perfluoro 3-heptyl group, perfluorooctyl group, perfluoro 2-methyl-2-octyl group, perfluorononyl group, perfluorodecyl group, perfluorophenyl group, perfluorohexyl group, perfluoropentyl group, perfluoroneopentyl group, perfluoro 2-methyl-2-pentyl group, perfluoro 2,4, 4-trimethyl-2-pentyl group, perfluorohexyl group, perfluoro 2-ethylhexyl group, perfluorocyclohexyl group, perfluorohexyl group, and the like, Perfluoro-2-methylphenyl group, perfluoro-3-methylphenyl group and perfluoro-4-methylphenyl group.
At R31And R32The number of fluorine atoms substituted with a hydrogen atom in the group is 1 to the maximum number which can be substituted, preferably 3 to the maximum number which can be substituted, more preferably 2 to the maximum number which can be substituted, still more preferably 1 to the maximum number which can be substituted, and particularly preferably the maximum number which can be substituted.
R31And R32More preferred are the same or different propyl, isopropyl, sec-butyl, 2-ethylhexyl and 4-tert-butylcyclohexyl groups.
R31And R32The same or different propyl and isopropyl groups are particularly preferred.
Preferred examples of the compound (C1) include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate.
Particularly preferred compounds (C1) are di-n-propylperoxydicarbonate and diisopropylperoxydicarbonate.
R33And R34Preferably, the same or different, are perfluoropropyl, perfluoroisopropyl, perfluoro 2-phenyl-2-propyl, perfluorobutyl, perfluoro sec-butyl, perfluoro tert-butyl, perfluoropentyl, perfluoroisopentyl, perfluoro neopentyl, perfluoro 2-methyl-2-pentyl, perfluoro 2,4, 4-trimethyl-2-pentyl, perfluorohexyl, perfluoro 2-methylhexyl, perfluoro 2-ethylhexyl, perfluorocyclohexyl, perfluoro 4-methylcyclohexyl, perfluoro 4-ethylcyclohexyl, perfluoro 4-tert-butylcyclohexyl, perfluoroheptyl, perfluoro 2-heptyl, perfluoro 3-heptyl, perfluorooctyl, perfluoro 2-methyl-2-octyl, perfluorononyl, perfluorodecyl, perfluoro alkyl, perfluoro 2-methyl-2-octyl, perfluoro 2-pentyl, perfluoro 2, 4-trimethyl-2-pentyl, perfluoro 2,4, 4-trimethyl-2-pentyl, perfluoro 2-hexyl, perfluoro 2-ethylhexyl, perfluoro 4-cyclohexyl, perfluoro 4-methylcyclohexyl, perfluoro 4-butylcyclohexyl, perfluoro 2-heptyl, perfluoro 3-heptyl, perfluoro 2-octyl, perfluoro 2-nonyl, perfluoro 2-decyl, and the like, Perfluorophenyl, perfluoro-2-methylphenyl, perfluoro-3-methylphenyl, and perfluoro-4-methylphenyl.
At R33And R34In the above formula, the number of fluorine atoms substituted with a hydrogen atom is from 1 to the maximum number which can be substituted, preferably from 3 to the maximum number which can be substituted less than the maximum number which can be substituted, and more preferably from the maximum number which can be substitutedThe maximum number is 2 or less and the maximum number that can be substituted, and more preferably 1 or less and the maximum number that can be substituted.
R33And R34More preferably, the same or different, are isopropyl, 2,4, 4-trimethylpentyl, omega-hydro-dodecafluorohexyl, omega-hydro-hexadecafluorooctyl, phenyl and 3-methylphenyl.
Preferred examples of the compound (C2) include diisobutyl peroxide, bis (3,5, 5-trimethylhexanoyl) peroxide, bis (omega-hydro-dodecafluoroheptanoyl) peroxide, bis (omega-hydro-hexadecafluorononoyl) peroxide, omega-hydro-dodecafluoroheptanoyl-omega-hydroxyhexadecafluorononoyl peroxide, benzoyl peroxide m-methylbenzoyl peroxide, m-toluoyl peroxide.
Particularly preferred compounds (C2) are diisobutyl peroxide, di (omega-hydro-dodecafluoroheptanoyl) peroxide, di (omega-hydro-hexadecafluorononoyl) peroxide, omega-hydro-dodecafluoroheptanoyl peroxide-omega-hydro-hexadecafluorononoyl peroxide and benzoyl peroxide.
R35And R36Preferably identical or different, a perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro 2-phenyl-2-propyl group, perfluorobutyl group, perfluorosec-butyl group, perfluoro tert-butyl group, perfluoropentyl group, perfluoroisopentyl group, perfluoroneopentyl group, perfluoro 2-methyl-2-pentyl group, perfluoro 2,4, 4-trimethyl-2-pentyl group, perfluorohexyl group, perfluoro 2-methylhexyl group, perfluoro 2-ethylhexyl group, perfluorocyclohexyl group, perfluoro 4-methylcyclohexyl group, perfluoro 4-ethylcyclohexyl group, perfluoro 4-tert-butylcyclohexyl group, perfluoroheptyl group, perfluoro 2-heptyl group, perfluoro 3-heptyl group, perfluorooctyl group, perfluoro 2-methyl-2-octyl group, perfluorononyl group, perfluorohexyl group, and the like, Perfluorodecyl, perfluorophenyl, perfluoro 2-methylphenyl, perfluoro 3-methylphenyl, and perfluoro 4-methylphenyl.
At R35And R36In the above formula, the number of fluorine atoms substituted with a hydrogen atom is from 1 to the maximum number which can be substituted, preferably from 3 to the maximum number which can be substituted, more preferably from 2 to the maximum number which can be substituted, and still more preferably from less than the maximum number which can be substituted1 to the maximum number that can be substituted, with the maximum number that can be substituted being particularly preferred.
R35And R36More preferably, the same or different, are isopropyl group, 2-phenyl-2-propyl group, tert-butyl group, 2-methyl-2-pentyl group, 2,4, 4-trimethyl-2-pentyl group, 2-heptyl group, 2-methyl-2-octyl group, phenyl group and 3-methylphenyl group.
Preferred examples of the compound (C3) include t-butyl peroxyneodecanoate, t-butyl peroxypivalate, t-hexyl peroxypivalate, OO-t-butyl O-isopropyl peroxycarbonate and t-butyl peroxyacetate.
Particularly preferred compounds (C3) are tert-butyl peroxypivalate and tert-hexyl peroxypivalate.
Preferred examples of the inorganic peroxide include ammonium, sodium and potassium salts of persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, percarbonic acid, permanganic acid.
Particularly preferred inorganic peroxides are ammonium persulfate, sodium persulfate and potassium persulfate.
The inorganic peroxides may be used alone, or 2 or more kinds may be used in combination. In addition, the inorganic peroxide can be used in combination with a sulfite-based reducing agent (e.g., sodium dithionite), a sulfite reducing agent (e.g., sodium sulfite, ammonium sulfite, and sodium bisulfite), and the like.
Preferred examples of the polymerization initiator include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, diisobutyl peroxide, di (ω -hydro-dodecafluoroheptanoyl) peroxide, di (ω -hydro-hexadecafluorononoyl) peroxide, ω -hydro-dodecafluoroheptanoyl- ω -hydrocyclohexadecanoyl, benzoyl peroxide, t-butyl peroxypivalate, t-hexyl peroxypivalate, ammonium persulfate, sodium persulfate, and potassium persulfate.
Particularly preferred polymerization initiators are di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, diisobutyl peroxide, di (omega-hydro-dodecafluoroheptanoyl) peroxide, benzoyl peroxide, t-butyl peroxypivalate, t-hexyl peroxypivalate, and ammonium persulfate.
The amount of the monomer (M) used in the polymerization reaction can be appropriately determined depending on the ratio of the structural unit corresponding to the monomer (M) in the fluoropolymer (a) to be obtained, and the like. For example, the amount is 50 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 100 mol% based on the total number of moles of all raw material monomers.
When other monomers than the monomer (M) are used, the amount of the other monomers in the desired fluoropolymer (A) can be appropriately determined depending on the proportion of the structural units corresponding to the other monomers, and the like. For example, the content is 50 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less, and particularly preferably 0 mol% relative to the total number of moles of all raw material monomers.
The amount of the aprotic solvent (B) used in the polymerization reaction is in the range of 20 to 300 mass%, preferably in the range of 35 to 250 mass%, and more preferably in the range of 50 to 300 mass% when the amount of the monomer (M) is 100 mass%. The amount of the polymerization initiator used in the polymerization reaction is, for example, in the range of 0.0001g to 0.05g, preferably in the range of 0.0001g to 0.01g, and more preferably in the range of 0.0005g to 0.008g, relative to 1g of all monomers used in the reaction (i.e., the total amount of the monomer (M) and other monomers).
The temperature of the polymerization reaction may be, for example, in the range of-10 ℃ to 160 ℃, preferably in the range of 0 ℃ to 160 ℃, and more preferably in the range of 0 ℃ to 100 ℃.
The polymerization reaction may be carried out at a temperature which is 20 ℃ or lower higher than the boiling point lower than either one of the monomer (M) corresponding to the structural unit as the main component of the fluoropolymer (a) and the aprotic solvent and which is 20 ℃ or lower than the 10-hour half-life temperature of the polymerization initiator. In this case, the lower limit of the temperature may be, for example, -10 ℃, preferably 0 ℃.
The reaction time of the polymerization reaction is preferably in the range of 0.5 to 72 hours, more preferably in the range of 1 to 48 hours, and still more preferably in the range of 3 to 30 hours.
The polymerization reaction may be carried out in the presence or absence of an inert gas (e.g., nitrogen), and is preferably carried out in the presence of an inert gas.
The polymerization reaction is carried out under reduced pressure, under atmospheric pressure, or under pressurized conditions.
The polymerization reaction can be carried out by adding the monomer to the aprotic solvent (B) containing a polymerization initiator. Further, the polymerization can be achieved by adding a polymerization initiator to the monomer-containing aprotic solvent (B).
The fluoropolymer (A) produced in the polymerization reaction can be isolated or purified by a conventional method such as extraction, dissolution, concentration, filtration, precipitation, dehydration, adsorption, chromatography, or a combination thereof, if necessary.
The fluoropolymer (a) is generally of low solubility relative to the aprotic solvent (B). Therefore, it is difficult to form a coating film or the like containing the fluoropolymer (A) at a high concentration. However, in the production method of the present invention, a liquid in which the fluoropolymer (a) is dissolved in a high concentration in the aprotic solvent (B) can be produced. For example, a liquid can be produced in which the amount of the fluoropolymer (a) dissolved is 20 mass% or more, preferably in the range of 20 to 65 mass%, more preferably in the range of more than 20 to 65 mass%, and particularly preferably in the range of more than 20 to 50 mass%, based on the total mass of the fluoropolymer (a) and the aprotic solvent (B).
The fluoropolymer (A) can be purified and separated from the liquid. In other embodiments, the liquid may be used directly in applications where fluoropolymer (a) is desired.
When the fluoropolymer (a) is the fluoropolymer (A3), the amount of the fluoropolymer (A3) dissolved may be, for example, 20 mass% or more, 30 mass% or more, more than 30 mass% or 31 mass% or more, preferably in the range of 20 to 65 mass%, more preferably in the range of 30 to 65 mass%, in the range of 31 to 65 mass%, particularly preferably in the range of 30 to 50 mass%, or in the range of 31 to 50 mass%, relative to the total mass of the fluoropolymer (A3) and the aprotic solvent (B).
When the fluoropolymer (a) is the fluoropolymer (A3) and the aprotic solvent is a non-perfluorinated solvent, the amount of the fluoropolymer (A3) dissolved may be less than 20% by mass, other than the above-mentioned ranges, for example, 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 30% by mass or more, more than 30% by mass, or 31% by mass or more, preferably 20% by mass or more and 65% by mass or less, more than 20% by mass and 65% by mass or less, or 20% by mass or more and 50% by mass or more, more preferably 30% by mass or more and 65% by mass or less, or 31% by mass or more and 65% by mass, particularly preferably 30% by mass or more and 50% by mass or less, or, Within a range of 31 to 50 mass%.
The fluoropolymer (a) produced by the production method (a) according to the present disclosure can be used for conventionally known applications of the fluoropolymer (a). Examples of such applications include a pellicle film formed on a photomask used in a photolithography process.
The embodiments described above are illustrative, and it is to be understood that various changes in form, detail, and the like may be made without departing from the spirit and scope of the invention.
Examples
One embodiment of the present disclosure is described below more specifically by way of examples, but the present disclosure is not limited thereto.
The symbols and abbreviations in the examples are used in the following sense.
PMMA: polymethyl methacrylate
Initiator solution (1): methanol solution containing 50 wt% of di-n-propyl peroxydicarbonate (10-hour half-life temperature: 40 ℃ C.)
Initiator solution (2): perfluorohexane solution containing 7 wt% of bis (omega-hydro-dodecafluoroheptanoyl) peroxide (10 h half-life temperature: 15 ℃)
Fluoropolymer (A3-1): polymer formed from structural unit (A3-1)
GPC analysis method
< sample Conditioning method >
The polymer was dissolved in perfluorobenzene to prepare a2 wt% polymer solution, which was made into a sample solution through a membrane filter (0.22 μm).
< measuring method >
Molecular weight standard sample: PMMA
The detection method comprises the following steps: RI (differential refractometer)
Criterion for polymer solubility
Whether or not the polymer is dissolved in the composition is judged as follows.
The prepared composition was visually confirmed to have no undissolved polymer, and the composition was judged to be dissolved when it flowed uniformly as a whole at room temperature.
Example 1: production of composition containing As Main component the structural Unit (A3-1)
A glass container (50 mL) was charged with 10g of the monomer (M3-1), 15g of methyl nonafluorobutyl ether as a solvent, and 0.017g of the initiator solution (1), and then heated to an internal temperature of 40 ℃ to carry out a polymerization reaction for 20 hours, thereby obtaining a composition containing 8.5g (Mw: 273268) of the fluoropolymer (A3-1) and 36 wt%. The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by removing unreacted raw materials, solvents, initiator residues, and trace impurities contained in the monomers after completion of the polymerization reaction (wherein, the impurities mean HF, 4,4, 5-trifluoro-2, 5-bis (trifluoromethyl) -1, 3-dioxolane, 2- (difluoromethyl) -2,4,4, 5-tetrafluoro-5- (trifluoromethyl) -1, 3-dioxolane, 4,4, 5-trifluoro-2, 5-bis (trifluoromethyl) -1, 3-dioxolane-2-carboxylic acid, and the like, and the same applies to other examples) by vacuum drying distillation at 120 ℃.
Example 2: production of composition containing As Main component the structural Unit (A3-1)
10g of the monomer (M3-1), 20g of methyl nonafluorobutyl ether as a solvent, and 0.030g of the initiator solution (1) were charged into a 50mL glass vessel, and then heated to an internal temperature of 40 ℃ for 20 hours to effect polymerization, thereby obtaining a composition containing 31 wt% of the fluoropolymer (A3-1)8.8g (Mw: 143514). The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue and trace impurities contained in the monomer after the completion of the polymerization reaction.
Example 3: production of composition containing As Main component the structural Unit (A3-1)
10g of the monomer (M3-1), 20g of methyl nonafluorobutyl ether as a solvent and 0.041g of the initiator solution (1) were charged into a 50mL glass vessel, and then heated to an internal temperature of 40 ℃ to carry out a polymerization reaction for 20 hours, thereby obtaining a composition containing 31 wt% of the fluoropolymer (A3-1) (Mw: 107403). The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 4: production of composition containing As Main component the structural Unit (A3-1)
A glass 50mL container was charged with 10g of the monomer (M3-1), 30g of methyl nonafluorobutyl ether as a solvent, and 0.017g of the initiator solution (1), and then heated to 40 ℃ for 20 hours to effect polymerization, thereby obtaining a composition containing 23 wt% of the fluoropolymer (A3-1)9.0g (Mw: 147399). The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 5: production of composition containing As the Main component the structural Unit (A3-1)
A monomer (M3-1) (10 g), methyl nonafluorobutyl ether (60 g) as a solvent, and an initiator solution (1) (0.013 g) were charged into a 50mL glass vessel, and then the mixture was heated to an internal temperature of 40 ℃ to conduct polymerization for 20 hours, thereby obtaining a composition containing 11 wt% of the fluoropolymer (A3-1) (7.4 g, Mw: 99273). The solubility of the polymer was visually confirmed to be a completely uniform solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue and trace impurities contained in the monomer after the completion of the polymerization reaction.
Example 6: production of composition containing As Main component the structural Unit (A3-1)
A monomer (M3-1) (10 g), methyl nonafluorobutyl ether (60 g) as a solvent, and an initiator solution (1) (0.013 g) were charged into a 50mL glass vessel, and then the mixture was heated to an internal temperature of 40 ℃ to conduct polymerization for 20 hours, thereby obtaining a composition containing 6.1g (Mw: 82991) of the fluoropolymer (A3-1) and 7 wt%. The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 7: production of composition containing As Main component the structural Unit (A3-1)
A glass container (50 mL) was charged with 10g of the monomer (M3-1), 5g of ethyl nonafluorobutyl ether (boiling point: 76 ℃ C.) as a solvent, and 0.020g of the initiator solution (1), and then heated to an internal temperature of 40 ℃ to carry out polymerization for 20 hours to give a composition containing 8.7g (Mw: 114791) of the fluoropolymer (A3-1) and 64 wt%. The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 8: production of composition containing As Main component the structural Unit (A3-1)
A glass container (50 mL) was charged with 10g of the monomer (M3-1), 12g of ethyl nonafluorobutyl ether as a solvent, and 0.015g of the initiator solution (1), and then heated to an internal temperature of 40 ℃ to carry out polymerization for 20 hours, thereby obtaining a composition containing 44 wt% of the fluoropolymer (A3-1) (Mw: 150609). The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 9: production of composition containing As Main component the structural Unit (A3-1)
A glass 50mL container was charged with 10g of the monomer (M3-1), 12g of ethyl nonafluorobutyl ether as a solvent, and 0.035g of the initiator solution (1), and then the mixture was heated to 40 ℃ for 20 hours to effect polymerization, thereby obtaining a composition containing 9.7g (Mw: 127901) of the fluoropolymer (A3-1) and 45 wt%. The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 10: production of composition containing As Main component the structural Unit (A3-1)
10g of the monomer (M3-1), 12g of ethylnonafluorobutyl ether as a solvent, and 0.054g of the initiator solution (1) were charged into a 50mL glass vessel, and then heated to an internal temperature of 40 ℃ to conduct polymerization for 20 hours, thereby obtaining a composition containing 9.7g (Mw: 113366) of the fluoropolymer (A3-1) and 45 wt%. The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 11: production of composition containing As Main component the structural Unit (A3-1)
10g of the monomer (M3-1), 20g of ethyl nonafluorobutyl ether as a solvent, and 0.041g of the initiator solution (1) were charged into a 50mL glass vessel, and then the vessel was heated to 40 ℃ to conduct polymerization for 20 hours, whereby a composition containing 31 wt% of the fluoropolymer (A3-1)9.0g (Mw: 97533) was prepared. The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue and trace impurities contained in the monomer after the completion of the polymerization reaction.
Example 12: production of composition containing As Main component the structural Unit (A3-1)
10g of the monomer (M3-1), 30g of ethyl nonafluorobutyl ether as a solvent, and 0.041g of the initiator solution (1) were charged into a 50mL glass vessel, and then the vessel was heated to 40 ℃ to conduct polymerization for 20 hours, whereby a composition containing 8.6g (Mw: 63291) of the fluoropolymer (A3-1) and 22 wt% was obtained. The solubility of the polymer was visually confirmed to be a completely uniform solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 13: production of composition containing As Main component the structural Unit (A3-1)
A glass 50mL container was charged with 10g of the monomer (M3-1), 60g of ethyl nonafluorobutyl ether as a solvent, and 0.020g of the initiator solution (1), and then heated to 40 ℃ for 20 hours to effect polymerization, thereby obtaining a composition containing 7.0g (Mw: 73154) of the fluoropolymer (A3-1) and 10 wt%. The solubility of the polymer was visually confirmed to be a completely uniform solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 14: production of composition containing As Main component the structural Unit (A3-1)
A monomer (M3-1) (10 g), ethylnonafluorobutyl ether (80 g) as a solvent, and an initiator solution (1) (0.020 g) were charged in a 50mL glass vessel, and then the vessel was heated to an internal temperature of 40 ℃ to conduct polymerization for 20 hours, thereby obtaining a composition containing 5.5g (Mw: 52838) of the fluoropolymer (A3-1) and 6 wt%. The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 15: production of composition containing As Main component the structural Unit (A3-1)
10g of the monomer (M3-1), 20g of 3-methoxytridecafluorohexane (boiling point: 98 ℃ C.) as a solvent, and 0.034g of the initiator solution (1) were charged into a 50mL glass vessel, and then the vessel was heated to an internal temperature of 40 ℃ to conduct polymerization for 20 hours, thereby obtaining a composition containing 31 wt% of the fluoropolymer (A3-1)8.9g (Mw: 131202). The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 16: production of composition containing As Main component the structural Unit (A3-1)
A glass container (50 mL) was charged with 10g of the monomer (M3-1), 15g of perfluorotripropylamine (boiling point: 128 ℃ C.) as a solvent, and 0.052g of the initiator solution (1), and then heated to 40 ℃ for 20 hours to effect polymerization, thereby obtaining a composition containing 37 wt% of the fluoropolymer (A3-1) (Mw: 158427) in an amount of 8.9 g. The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 17: production of composition containing As Main component the structural Unit (A3-1)
A20 mL glass vessel was charged with 10g of the monomer (M3-1), 10g of perfluorotripropylamine as a solvent, and 0.052g of the initiator solution (1), and then heated to 40 ℃ for 20 hours to polymerize the monomer, thereby obtaining a composition containing 49 wt% of the fluoropolymer (A3-1)9.5g (Mw: 213475). The solubility of the polymer was visually confirmed to be a completely uniform solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 18: production of composition containing As the Main component the structural Unit (A3-1)
A20 mL glass vessel was charged with 10g of the monomer (M3-1), 15g of perfluoro-5-butyltetrahydrofuran (boiling point: 102 ℃ C.) as a solvent, and 0.025g of the initiator solution (1), and then heated to an internal temperature of 40 ℃ to carry out polymerization for 20 hours, thereby obtaining a composition containing 38 wt% of the fluoropolymer (A3-1)9.0g (Mw: 158992). The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 19: production of composition containing As Main component the structural Unit (A3-1)
A20 mL glass vessel was charged with 10g of the monomer (M3-1), 10g of perfluorohexane (boiling point: 56 ℃ C.) as a solvent, and 0.025g of the initiator solution (1), and then the mixture was heated to an internal temperature of 40 ℃ to carry out polymerization for 20 hours, thereby obtaining a composition containing 8.2g (Mw: 128122) of the fluoropolymer (A3-1) and 45 wt%. The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue and trace impurities contained in the monomer after the completion of the polymerization reaction.
Example 20: production of composition containing As Main component the structural Unit (A3-1)
A20 mL glass vessel was charged with 10g of the monomer (M3-1), 10g of perfluorobenzene (boiling point: 80 ℃ C.) as a solvent, and 0.031g of the initiator solution (1), and then the mixture was heated to an internal temperature of 40 ℃ to conduct polymerization for 20 hours, thereby obtaining a composition containing the fluoropolymer (A3-1) in an amount of 4.7g (Mw: 45323) and having a content of 32 wt%. The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 21: production of composition containing As Main component structural Unit (A3-1)
A20 mL glass vessel was charged with 10g of the monomer (M3-1), 20g of methyl nonafluorobutyl ether as a solvent, and 0.010g of the initiator solution (2), and then, polymerization was carried out for 20 hours while adjusting the temperature to 15 ℃ to obtain a composition containing 9.3g (Mw: 217533) of the fluoropolymer (A3-1) and 32 wt%. The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 22: production of composition containing As Main component structural Unit (A3-1)
A glass container (20 mL) was charged with 10g of the monomer (M3-1), 20g of methyl nonafluorobutyl ether as a solvent, and 0.022g of the initiator solution (2), and then polymerization was carried out for 20 hours while adjusting the temperature to 15 ℃ to obtain a composition containing 9.6g (Mw: 109215) of the fluoropolymer (A3-1) and 32 wt%. The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 23: production of composition containing As Main component the structural Unit (A3-1)
A20 mL glass vessel was charged with 10g of the monomer (M3-1), 15g of perfluorotripropylamine as a solvent, and 0.017g of the initiator solution (2), and then the mixture was polymerized for 20 hours while adjusting the temperature to 15 ℃ to obtain a composition containing 8.6g (Mw: 163900) of the fluoropolymer (A3-1) and 36 wt%. The solubility of the polymer was visually confirmed to be a completely uniform solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 24: production of composition containing As Main component the structural Unit (A3-1)
A monomer (M3-1) (10 g), 1,1,2,3, 3-hexafluoropropyl methyl ether (15 g) as a solvent and 0.041g of an initiator solution (1) were charged into a 50mL glass vessel, and polymerization was carried out for 20 hours while the temperature was adjusted to 40 ℃ to obtain a composition containing 37 wt% of the fluoropolymer (A3-1) (9.3 g, Mw: 99264). The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 25: production of composition containing As Main component the structural Unit (A3-1)
A glass 50mL container was charged with 10g of the monomer (M3-1), 20g of 1,1,1,2,3, 3-hexafluoropropyl methyl ether as a solvent, and 0.037g of the initiator solution (1), and then, polymerization was carried out for 20 hours while adjusting the temperature to 40 ℃ to obtain a composition containing 30 wt% of the fluoropolymer (A3-1)8.9g (Mw: 80192). The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 26: production of composition comprising As Main component the structural Unit (A3-1)
A monomer (M3-1) (10 g), 1,1,2,3, 3-hexafluoropropyl methyl ether (20 g) as a solvent and an initiator solution (2) (0.025 g) were charged into a 50mL glass vessel, and polymerization was carried out for 20 hours while the temperature was adjusted to 15 ℃ to obtain a composition containing a fluoropolymer (A3-1) (9.4 g, Mw: 102931) and 31 wt%. The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 27: production of composition containing As Main component the structural Unit (A3-1)
A glass 50mL container was charged with 10g of the monomer (M3-1), 15g of 1,1,2, 2-tetrafluoroethyl 2,2, 2-trifluoroethyl ether as a solvent, and 0.040g of the initiator solution (1), and then polymerization was carried out for 20 hours while adjusting the temperature to 40 ℃ to obtain a composition containing 36 wt% of the fluoropolymer (A3-1)8.9g (Mw: 110481). The solubility of the polymer was visually confirmed to be a completely uniform solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 28: production of composition containing As Main component the structural Unit (A3-1)
A glass 50mL container was charged with 10g of the monomer (M3-1), 20g of 1,1,2, 2-tetrafluoroethyl 2,2, 2-trifluoroethyl ether as a solvent, and 0.034g of the initiator solution (1), and then, polymerization was carried out for 20 hours while adjusting the temperature to 40 ℃ to obtain a composition containing 29 wt% of the fluoropolymer (A3-1)8.6g (Mw: 97423). The solubility of the polymer was visually confirmed to be a completely uniform solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 29: production of composition containing As Main component the structural Unit (A3-1)
A monomer (M3-1) (10 g), 1,2, 2-tetrafluoroethyl 2,2, 2-trifluoroethyl ether (20 g) as a solvent and 0.023g of an initiator solution (2) were put into a 50mL glass vessel, and polymerization was carried out for 20 hours while adjusting the temperature to 15 ℃ to obtain a composition containing 31 wt% of a fluoropolymer (A3-1) (9.2 g, Mw: 126345). The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 30: production of composition containing As Main component the structural Unit (A3-1)
A glass 50mL container was charged with 10g of the monomer (M3-1), 15g of 1,1,1,3,3, 3-hexafluoro-2-methoxypropane as a solvent, and 0.040g of the initiator solution (1), and then polymerization was carried out for 20 hours while adjusting the temperature to 40 ℃ to obtain a composition containing 34 wt% of the fluoropolymer (A3-1)8.4g (Mw: 78016). The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 31: production of composition containing As Main component the structural Unit (A3-1)
A glass 50mL container was charged with 10g of the monomer (M3-1), 20g of 1,1,1,3,3, 3-hexafluoro-2-methoxypropane as a solvent, and 0.036g of the initiator solution (1), and then, polymerization was carried out for 20 hours while adjusting the temperature to 40 ℃ to obtain a composition containing 26 wt% of the fluoropolymer (A3-1)7.9g (Mw: 70127). The solubility of the polymer was visually confirmed to be a completely uniform solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
Example 32: production of composition containing As Main component the structural Unit (A3-1)
A50 mL glass vessel was charged with 10g of the monomer (M3-1), 20g of 1,1,1,3,3, 3-hexafluoro-2-methoxypropane as a solvent, and 0.022g of the initiator solution (2), and then polymerization was carried out for 20 hours while adjusting the temperature to 15 ℃ to obtain a composition containing 8.9g (Mw: 84829) of the fluoropolymer (A3-1) and 30 wt%. The solubility of the polymer was visually confirmed to be a completely homogeneous solution.
The weight of the polymer in the composition was measured by vacuum drying at 120 ℃ and distilling off unreacted raw materials, solvent, initiator residue, and trace impurities contained in the monomer after completion of the polymerization reaction.
The results obtained in the examples are shown in tables 1 and 2.
[ Table 1]
Figure BDA0003627434700000441
[ Table 2]
Figure BDA0003627434700000451

Claims (42)

1. A composition characterized by:
comprising a fluorine-containing polymer (A) and an aprotic solvent (B), wherein the fluorine-containing polymer (A) contains a structural unit having a fluorine-containing aliphatic ring as a main component,
wherein the fluorine-containing alicyclic ring of the fluorine-containing polymer (A) has 1,2 or 3 ether-type oxygen atoms as ring-forming atoms, and when the fluorine-containing alicyclic ring contains a plurality of the ether-type oxygen atoms, the ether-type oxygen atoms are not adjacent to each other,
the content of the fluoropolymer (A) is 20% by mass or more based on the mass of the composition.
2. The composition of claim 1, wherein:
the content of the fluoropolymer (A) is within the range of 20 to 65% by mass relative to the mass of the composition.
3. The composition of claim 1 or 2, wherein:
the content of the fluoropolymer (A) is in the range of more than 20% by mass and not more than 65% by mass relative to the mass of the composition.
4. The composition of any one of claims 1 to 3, wherein:
the aprotic solvent (B) is at least one solvent selected from the group consisting of a perfluoroaromatic compound, a perfluorotrialkylamine, a perfluoroalkane, a hydrofluorocarbon, a perfluorocyclic ether, a hydrofluoroether, and an olefin compound containing at least one chlorine atom.
5. The composition of any one of claims 1 to 4, wherein:
the aprotic solvent (B) is a hydrofluoroether.
6. The composition of any one of claims 1 to 5, wherein:
the aprotic solvent (B) has a Global Warming Potential (GWP) of 400 or less.
7. The composition of any one of claims 1 to 6, wherein:
the aprotic solvent (B) is selected from the group consisting of a compound represented by the formula (B-1), a compound represented by the formula (B-2), a compound represented by the formula (B-3), a compound represented by the formula (B-4), and (CF)3)2CHOCH3、(CF3)2CFOCH3、CF3CHFCF2OCH3And CF3CHFCF2OCF3At least one hydrofluoroether of (a) at least one hydrofluoroether,
F(CF2)pO(CH2)qH (B-1)
wherein p is an integer of 1 to 6, and q is an integer of 1 to 4;
H(CF2)pO(CF2)qF (B-2)
wherein p and q have the same meanings as described above;
H(CF2)pO(CH2)qH (B-3)
wherein p and q have the same meanings as described above;
X(CF2)pCH2O(CF2)qH (B-4)
wherein X represents a fluorine atom or a hydrogen atom, and p and q have the same meanings as described above.
8. The composition of any one of claims 1 to 7, wherein:
the aprotic solvent (B) is a compound represented by the formula (B-5),
R21-O-R22 (B-5)
in the formula, R21Is a linear or branched propyl or butyl group having one or more hydrogen atoms replaced by fluorine atoms, R22Is methyl or ethyl.
9. The composition of any one of claims 1 to 8, wherein:
the fluorine-containing aliphatic ring of the fluorine-containing polymer (A) is a 4-, 5-, 6-or 7-membered ring.
10. The composition of any one of claims 1 to 9, wherein:
the fluorine-containing polymer (A) contains, as a main component, a structural unit represented by the following formula (A1), a structural unit represented by the following formula (A2), or a structural unit represented by the following formula (A3),
Figure FDA0003627434690000021
in the formula, R1A perfluoroalkyl group having a fluorine atom or C1-C5;
Figure FDA0003627434690000031
in the formula, R2～R5Independently represent a fluorine atom, a perfluoroalkyl group having C1 to C5, or a perfluoroalkoxy group having C1 to C5;
Figure FDA0003627434690000032
in the formula, R6～R9Independently represent a fluorine atom, a perfluoroalkyl group having C1 to C5 or a perfluoroalkoxy group having C1 to C5.
11. The composition according to any one of claims 1 to 10, wherein:
the fluorine-containing polymer (A) contains a structural unit represented by the formula (A3) as a main component.
12. The composition of any one of claims 1,4 to 8, wherein:
the fluorine-containing polymer (A) is the fluorine-containing polymer (A) other than the polymer containing the structural unit represented by the formula (A3) as a main component,
the content of the fluorine-containing polymer (A) is 30% by mass or more relative to the mass of the composition.
13. The composition of claim 12, wherein:
the content of the fluoropolymer (A) is more than 30% by mass based on the mass of the composition.
14. The composition of any one of claims 1 to 10, wherein:
the fluorine-containing polymer (A) contains, as a main component, a structural unit represented by the following formula (A1-1), a structural unit represented by the following formula (A2-1), a structural unit represented by the following formula (A2-2) or a structural unit represented by the following formula (A3-1),
Figure FDA0003627434690000041
15. the composition of claim 11, wherein:
the fluorine-containing polymer (A) contains a structural unit represented by the formula (A3-1) as a main component.
16. The composition of claim 12 or 13, wherein:
the fluorine-containing polymer (A) contains, as a main component, a structural unit represented by the formula (A1-1), a structural unit represented by the formula (A2-1), or a structural unit represented by the formula (A2-2).
17. The composition of any one of claims 1 to 16, wherein:
the fluoropolymer (A) has a mass average molecular weight of 5000 to 1000000.
18. The composition of any one of claims 1 to 17, wherein:
the mass average molecular weight of the fluorine-containing polymer (A) is 40000-500000.
19. A method of manufacture, characterized by:
the method for producing a fluorine-containing polymer (A) containing a structural unit having a fluorine-containing alicyclic ring as a main component by polymerizing a monomer in the presence of a polymerization initiator,
wherein the fluorine-containing alicyclic ring of the fluorine-containing polymer (A) has 1,2 or 3 ether-type oxygen atoms as ring-forming atoms, and when the fluorine-containing alicyclic ring contains a plurality of the ether-type oxygen atoms, the ether-type oxygen atoms are not adjacent to each other,
the monomer includes a monomer (M) corresponding to a structural unit contained as a main component in the fluoropolymer (A),
the polymerization is carried out in an aprotic solvent (B),
the aprotic solvent (B) is at least one solvent selected from the group consisting of a perfluoroaromatic compound, a perfluorotrialkylamine, a perfluoroalkane, a perfluorocyclic ether, a hydrofluoroether, and an olefin compound containing at least one chlorine atom.
20. The manufacturing method according to claim 19, wherein:
the polymerization initiator has a 10-hour half-life temperature in the range of 0 ℃ to 160 ℃, and the polymerization reaction is carried out in the aprotic solvent (B) under conditions of a temperature not higher than 20 ℃ higher than the boiling point lower than either of the monomer (M) and the aprotic solvent, and not higher than 20 ℃ higher than the 10-hour half-life temperature of the polymerization initiator.
21. The manufacturing method according to claim 19 or 20, wherein:
the polymerization initiator is a non-perfluorinated polymerization initiator.
22. The manufacturing method according to any one of claims 19 to 21, wherein:
the polymerization initiator is at least one selected from the group consisting of a compound represented by the formula (C1), a compound represented by the formula (C2), a compound represented by the formula (C3), and an inorganic peroxide,
Figure FDA0003627434690000051
in the formula, R31And R32The same or different, and is a group in which at least one fluorine atom in a C3-C10 perfluoroalkyl group which may be substituted with a perfluorophenyl group is substituted with a hydrogen atom, and a group in which at least one fluorine atom in a perfluorophenyl group which may be substituted with a linear or branched C1-C4 perfluoroalkyl group is substituted with a hydrogen atom;
Figure FDA0003627434690000061
in the formula, R33And R34The same or different, and is a group in which at least one fluorine atom in a C3-C10 perfluoroalkyl group which may be substituted with a perfluorophenyl group is substituted with a hydrogen atom, and a group in which at least one fluorine atom in a perfluorophenyl group which may be substituted with a linear or branched C1-C4 perfluoroalkyl group is substituted with a hydrogen atom;
Figure FDA0003627434690000062
in the formula, R35And R36The perfluoroalkyl group may be a perfluoroalkyl group having 1 to 10 and substituted with a perfluorophenyl group, in which at least one fluorine atom is replaced with a hydrogen atom, or a perfluoroalkyl group having 1 to 4 and substituted with a linear or branched perfluoroalkyl group, in which at least one fluorine atom is replaced with a hydrogen atom.
23. The manufacturing method according to any one of claims 19 to 22, wherein:
the aprotic solvent (B) is hydrofluoroether.
24. The production method according to any one of claims 19 to 23, wherein:
the aprotic solvent (B) has a Global Warming Potential (GWP) of 400 or less.
25. The manufacturing method according to any one of claims 19 to 24, wherein:
the aprotic solvent (B) is selected from the group consisting of a compound represented by the formula (B-1), a compound represented by the formula (B-2), a compound represented by the formula (B-3), a compound represented by the formula (B-4), and (CF)3)2CHOCH3、(CF3)2CFOCH3、CF3CHFCF2OCH3And CF3CHFCF2OCF3ToAt least one kind of hydrofluoroether is used as the active ingredient,
F(CF2)pO(CH2)qH (B-1)
wherein p is an integer of 1 to 6, and q is an integer of 1 to 4;
H(CF2)pO(CF2)qF (B-2)
wherein p and q have the same meanings as described above;
H(CF2)pO(CH2)qH (B-3)
wherein p and q have the same meanings as described above;
X(CF2)pCH2O(CF2)qH (B-4)
wherein X represents a fluorine atom or a hydrogen atom, and p and q have the same meanings as described above.
26. The manufacturing method according to any one of claims 19 to 25, wherein:
the aprotic solvent (B) is a compound represented by the formula (B-5),
R21-O-R22 (B-5)
in the formula, R21Is a straight-chain or branched propyl or butyl group having one or more hydrogen atoms substituted by fluorine atoms, R22Is methyl or ethyl.
27. The production method according to any one of claims 19 to 26, wherein:
the amount of the aprotic solvent (B) in the polymerization reaction is in the range of 20 to 300 mass% with respect to the mass of the monomer (M).
28. The method according to any one of claims 19 to 27, wherein:
the amount of the aprotic solvent (B) in the polymerization reaction is in the range of 50 to 200 mass% with respect to the mass of the monomer (M).
29. The production method according to any one of claims 19 to 28, wherein:
the fluorine-containing aliphatic ring of the fluorine-containing polymer (A) is a 4-, 5-, 6-or 7-membered ring.
30. The manufacturing method according to any one of claims 19 to 29, wherein:
the fluorine-containing polymer (A) contains, as a main component, a structural unit represented by the following formula (A1), a structural unit represented by the following formula (A2), or a structural unit represented by the following formula (A3),
Figure FDA0003627434690000071
in the formula, R1A perfluoroalkyl group having a fluorine atom or C1-C5;
Figure FDA0003627434690000081
in the formula, R2～R5Independently represent a fluorine atom, a perfluoroalkyl group having C1 to C5, or a perfluoroalkoxy group having C1 to C5;
Figure FDA0003627434690000082
in the formula, R6～R9Independently represent a fluorine atom, a perfluoroalkyl group having C1 to C5 or a perfluoroalkoxy group having C1 to C5.
31. The production method according to any one of claims 19 to 30, wherein:
the fluorine-containing polymer (A) contains a structural unit represented by the formula (A3) as a main component.
32. The production method according to any one of claims 19 to 30, wherein:
the fluorine-containing polymer (A) is the fluorine-containing polymer (A) other than the polymer containing the structural unit represented by the formula (A3) as a main component.
33. The production method according to any one of claims 19 to 30, wherein:
the fluorine-containing polymer (A) contains, as a main component, a structural unit represented by the following formula (A1-1), a structural unit represented by the following formula (A2-1), a structural unit represented by the following formula (A2-2) or a structural unit represented by the following formula (A3-1),
Figure FDA0003627434690000083
Figure FDA0003627434690000091
34. the method of manufacturing of claim 31, wherein:
the fluorine-containing polymer (A) contains a structural unit represented by the formula (A3-1) as a main component.
35. The method of manufacturing of claim 32, wherein:
the fluorine-containing polymer (A) contains a structural unit represented by the formula (A1-1), a structural unit represented by the formula (A2-1) or a structural unit represented by the formula (A2-2) as a main component.
36. The manufacturing method according to any one of claims 19 to 35, wherein:
the fluoropolymer (A) has a mass average molecular weight of 5000 to 1000000.
37. The production method according to any one of claims 19 to 36, wherein:
the mass average molecular weight of the fluorine-containing polymer (A) is 40000-500000.
38. A composition characterized by:
comprising a fluorine-containing polymer (A) and an aprotic solvent (B), wherein the fluorine-containing polymer (A) contains a structural unit having a fluorine-containing aliphatic ring as a main component,
the fluorine-containing polymer (A) contains a structural unit represented by the following formula (A3) as a main component,
Figure FDA0003627434690000101
in the formula, R6～R9Independently represent a fluorine atom, a perfluoroalkyl group having C1 to C5 or a perfluoroalkoxy group having C1 to C5,
the aprotic solvent (B) is a non-perfluorinated solvent.
39. The composition of claim 38, wherein:
the non-perfluorinated solvent is a hydrofluoroether.
40. The composition of claim 38 or 39, wherein:
the non-perfluorinated solvent has a Global Warming Potential (GWP) of 400 or less.
41. The composition according to any one of claims 38 to 40, wherein:
the non-perfluorinated solvent is selected from the group consisting of a compound represented by the formula (B-1), a compound represented by the formula (B-2), a compound represented by the formula (B-3), a compound represented by the formula (B-4), and (CF)3)2CHOCH3、(CF3)2CFOCH3、CF3CHFCF2OCH3And CF3CHFCF2OCF3At least one hydrofluoroether of (a) at least one hydrofluoroether,
F(CF2)pO(CH2)qH (B-1)
wherein p is an integer of 1 to 6, and q is an integer of 1 to 4;
H(CF2)pO(CF2)qF (B-2)
wherein p and q have the same meanings as described above;
H(CF2)pO(CH2)qH (B-3)
wherein p and q have the same meanings as described above;
X(CF2)pCH2O(CF2)qH (B-4)
wherein X represents a fluorine atom or a hydrogen atom, and p and q have the same meanings as described above.
42. The composition according to any one of claims 38 to 41, wherein:
the non-perfluorinated solvent is a compound shown as a formula (B-5),
R21-O-R22 (B-5)
in the formula, R21Is a straight-chain or branched propyl or butyl group having one or more hydrogen atoms substituted by fluorine atoms, R22Is methyl or ethyl.
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